Radical addition reactions of halogenated olefins and compounds produced thereby



United States Patent Office RADICAL ADDITION REACTIONS OF HALO- GENATED OLEFINS AND; COMPOUNDS PRODUCED THEREBY William Miller, Ithaca, N.Y., assignor, by mesne, as-

signments, to Minnesota Mining and, Manufacturing Company, St. Paul, Minn, a corporation of Delaware N o Drawing. Application: July" 12, 1955. Serial N0. 521,638J

11 Claims; (Cl. 260-653) This invention relates to novel radical, addition re,- actions of polyand perhalogenated' alkanes, withrhalogenated ethylenically unsaturated compounds.

The principal reactions occurring in the process ofthe present invention are as follows, inwhich CX; is, a per.- halogenate alkane, i.e., a perhalogenatedmethanezj FREE RADICAL ADDITION OF OX; TO AN OLEFIN' [Principal reactions] I; I Initiation 1 R Q D:

chemical A, thermal (inthe case ot iodides) OX 3, (1X3; +x- QXH-R-(lrom peroxide) BX OX;

The initial free radicals are produced, by thetphotos chemical or thermal dissociation of, the halogenated methane or may be produced in any other conventional manner such as by the use of a peroxide catalyst, exemplary of such catalysts, being, acylr peroxides such as acetyl, benzoyl, and pelargonylperoxidesor other sources of free radicals such as the compound If theradicals. formed by the dissociation of the methane; do not attack the, olefin, the observed reaction products: are decomposition products derived from the methane; An example of this behavior is shown when an attempt is made to a-ddtrichloroiodomethane to hexafluorocycljobutene. The hexafluorocyclobutene is unchanged, and hexachloroethane and iodine, are;for;med;

The initiation step is, followedby' a propagation, step which can involve a, number-of-olefin,molecules for every initiation;- An initiating radical; can reachwith an; olefin molecule to form a ,newlarger radical, a processleading 2,880,247 Patented Mar. 31, 1959 Thisis, also the order which would be; predicted on the basis ofsten'c effect.

An attacking radical; Equation: 2 above, might attack either or both ends ofanunsymmetrical olefin with therformation, of either or both, of. the possible; addition products. It has, been; shown, however, that a, cleanecut orientation: effect is operative, in. free radical reactions involving, hydrogen-containing; olefins with only one of the; twopossible isomers being formed, Furthermore, in

- every case, the initial attack was on the most exposed position to yield the intermediate radical which was predicted to be the most. stable.

In the; present invention: thev following illustrative product was obtained from the unsymmetrical perhaloolefin:

Reactants Product This product'indicates that the initial attack by CX-gradicals is on the exposed CF carbon as the CCI'QF- radical adds to the CH carbon of, unsymmetrical difi'uoroethy-lene; This orientation is the one which would be predicted from stericconsiderations.

The alkanes which may be added to halogenated 01efins in accordance with the present invention are those having the formula:

in, which X may be fluorine, chlorine, or a poly-l or perhal'ogenated alkyl radical having not in excess of about 8 carbon atoms and in which all of the halogen atoms are fluorine or chlorine, and. X and X may he: fluorine-1 or chlorine, at. least one. of X and; X being chlorine. WherrX is a polyhalogenated radical, the; average, hydrogen. content is numerically no more than; the carbon content. Exemplary of such compounds are CCl I, CClF CC1FL. CC1F CCl I, and CCI FI;

'Ehe-olefinswhich may be used? in the process, of the invention arezthose having the formula in; Which- Y may be hydrogen, fluorine, chlorine; or-a;

saturated or unsaturated perhalogenatedv alkyl. radical having not in excess of l2:carbonatoms and in-which all; ofthe halogenatoms. of the alkyl, radical arerfluorine or, chlorine, Y may be hydrogen, fluorine or. chlorine andHY andY; may be, fluorine or chlorine, A t-least one of the Y substituents must be other than fluorine. Exemplary of the olefins contemplated are CClF=CF CF =CHCClFCF CF=CHF CF ClCH CCLFCF CF=CHF CF ClCH CCIFCF CF CH CF=CF and CFCl CF (CFClCF ),,CF=CF where "=1 to 10.

The most satisfactory olefins for radical addition reactions are the more reactive types, as evidenced by their polymerizability, provided effective chain transfer agents are utilized for addition. However, useful syntheses are also obtained with less reactive olefins which have not been satisfactorily polymerized alone and for which, although reaction occurs more slowly,. the simultaneous formation of polymer is not a problem. On the other hand, useful addition reactions are not obtained with disubstituted olefins of the general type R CF=CFR in which R is a perhalogenated group.

The most effective radical chain transfer compounds are iodides of the type RCCI I in which R is chlorine, fluorine, or a perhalogenated group, and excellent yields of monomer addition compounds are obtained by reaction of these iodides with the more reactive olefins. Mild reaction conditions and equivalent quantities of reactants CClFzC ClFC FzCClFI ethanol The replacement of iodine by hydrogen as a result of treatment with zinc and alcohol represents a useful new synthetic method.

Dehydrohalogenation may be employed to prepare halogenated alkenes from iodoalkanes as follows, in which 3,3-dichloro-1,1,3-trifiuoropropene is prepared from 1,1- dichloro-1,3,3-trifluoro-3-iodopropane, and the structure I of the propene is confirmed by oxidation:

The radical addition reactions of the invention may be effected using a molar ratio of polyor perhalogenated alkane to halogenated monoolefin in the range of 1 to 1, to 20to 1, a temperature in the range of to 250 C., preferably 20 to 200 C., and a reaction time of 30 seconds to 150 hours, preferably 0.5 to 2.5 hours. When a peroxide catalyst is used, it may be employed in a concentration of 0.1 to moles per 100 moles of olefin. The pressure may be in the range of 1 to 100 atmospheres, and is preferably autogenous. When diand triolefins, and the like, are used, the molar ratio of reactants is increased in favor of the alkane.

Also, in the present invention it was found that perhalogenated iodides, such as the compound CCIF CCI CF CCIFI can be coupled to form compounds such as (CCIF CCl CF CCIF) 2 This perhalogenated octane is the hexachloride of the unconjugated triene, CF =CClCF CF=CFCF CCl=CF a desired monomer material.

The products produced by the process of the invention are useful as solvents for fluorine-containing polymers, fire extinguishing agents, non-flammable hydraulic fluids,

For example, reduction and dehalogenation was:

lubricating oil additives, and chemical intermediates in the preparation of other compounds.

The invention will be further illustrated by reference to the following specific examples:

EXAMPLE 1 Reaction of C ClF I with zinc Ten grams of C ClF I were added slowly to a suspension of 15 grams of zinc dust in 30 ml. of refluxing commercial absolute enthanol. An exothermic reaction occurred, but no material boiling below 0 C. was collected. The product was distilled out of the reaction mixture, treated with P 0 to remove the alcohol, and distilled. The product, 4 grams, boiled at 18 C. at 735 mm. The infrared spectrum of this material showed a carbon-hydrogen peak. The isomeric CHF CF CCIF is reported to boil at 21 C.

This hydrogen-containing compound, presumed to be CF CF CHClF, was scaled up with chlorine and water and irradiated in a 5-bulb ultraviolet illuminator for 18 hours. The resulting compound was Washed with NaOH and water, then dried and distilled. The CF CF CCl F, 3 grams, boiled at 35-36 C. at 740 mm. The refractive index was n 1.312.

The structure was proven by the infrared spectrum, which was different from the spectra of the known CClF CF CClF (B.P. 36.1 C.; n 1.3027) and CC1F CClFCF (B.P. 34.8 C.; n 1.3034).

EXAMPLE 2 Free radical addition reaction of CC13I and CClF=CF A mixture of 66 grams of CClF=CF and 126 grams of CCl I' was placed in a Pyrex ampoule and illuminated for five days by 5 ultraviolet bulbs. The ampoule was opened and 8 parts of recovered unreacted CClF=CF were allowed to distill out. The remaining liquid was distilled at 10 mm. to yield:

(1) Solid carbon dioxide trap 18 grams. (2) B.P. 72 t0 74C./10

- 46 grams The properties of Fraction 7 were: B.P., 74.2 C./10 mm.; d 2.2265; n 1.5080; F.P. 50.1 C. MR found, 48.42; calculated, 48.48.

EXAMPLE 3 F luorination of CCl CF CClFI A sample of the addition product of CCl I and CClF=CF prepared in the manner of Example 2 above (250 grams), was placed in a steel bomb with 180 grams of SbF- and 72 grams of C1 The bomb was placed in a rocker-shaker and heated to :5 C. for twenty hours. The contents of the bomb, containing considerable free iodine, were steam distilled out of the bomb, steam distilled again to separate from the antimony salts and the bulk of the water, separated, dried over P 0 and distilled to yleld:

(1 B.P. 33 to 351 C 25 grams} 2 B.P. 35.1 to 352 0. 740 mm. 21 grams CBChFB 3i B.P. 35.2 to 36 c. 22 grams P 54) B.P. 36 to 72 C. 3 grams.

(5) B.P. 72 to 73.7 C. 20 grams (1 C] F (6) B.P. 73.7 to 733 C./737 mm. 21 grams 3 1 t (7) B.P. 73.8 to 74 C 12 grams Peru (8) Residue 11 grams.

EXAMPLE 4' Free radical-addition reaction of CCl CClFI and F=CF2 The optimum reaction procedure found for the addition of CClF CCIFI to CCIF=F consisted of heating a molar ratio. of iodide to olefin of 4 to 1 with approximately 3 mole percent of the olefin of benzoyl peroxide at 100 C. for three hours tofour'hours. In a typical run, three 1500 ml. stainless steel aviation type oxygen cylinders were filled with a total of 2451 grams of CCIF CCIFI and 20 grams of benzoyl peroxide. The cylinders were cooled in, solid carbon dioxide, evacuated, and a total of 259 grams of CF ==CCIF were condensed into them. They were heated in boiling water for the required time after which venting of the cylinders and distillation at reduced pressure (water pump) into a solid carbon dioxide trap yielded 67 grams of unreacted olefin, corresponding to a conversion of 74 percent. The light pink product was washed with aqueous sodium thiosulfate, dried, over calcium chloride and distilled rapidly through a Berl saddle packed Hemple column to yield 2048 grams of unreacted CClF CQlFI' and a residue of 477 grams. Distillation of thlsresidue yielded:

(1) B.P. 38-40" C./601nm. 65 grams (CClF CclFl).

(2) B.P. 60-6890 CL/20 mm. 190 grams (CClF 'CClFCF2CClFl) (3') B.P. 100424; C./10 mm. 20 grams.

(4) Residue 200 grams.

Fraction 3 was thoughtto be CClF CClF(CF CClF) I, but; it was not further investigated. The residue was a very viscous mass at room temperature and was presumed to consist of higher polymers. Fraction 2 had the predicted B.P. for C Cl F I and chemical and analytical properties of this fraction later confirmed this structure. The direction of addition was predicted on the basis of earlier work and was later confirmed by its conversion toCF =CFCF CHClF and not to CF =CFCF=CF by zip? in ethanol.

EXAMPLE 5 Purification of the crude C C1 F I A preliminary distillation of the butane fraction of Example 4 above showed that although the majority of the fraction had a very narrow boiling range, it contained considerable impurities as indicated by change in refractive index. The impurity was suspected to be iodobenzene, derived from benzoyl peroxide, whose boiling point was within a few degrees of the butane.

Fraction 2 of Example 4 above (140 grams) was slowly dropped into a 3-necked flask, containing 25 ml. of 30 percent fuming H SO equipped with reflux condenser, glass stirrer, and a dropping funnel. The mixturebecame warm (ca. 30-35 C.) but the temperature was easily controlled by the rate of addition (15 minutes). The mixture was stirred an additional 15 minutes at room temperature and finally 25 ml. of 95 percent H 80 were addedjand the whole mixture was drowned in water. The light: pink organic layer was washed once with water to give, a crude yield of 162 grams. The 28 gram loss in weight compares to the theoretical amount of iodo benzene of 3.1 g ramsif all the peroxide had been con-. verted'into this product:

The product was dried" over magnesium sulfate, and distilled to yield:

(1) B.P. 4070 C./18 mm. 47' grams.

2 B.P. 70.5,-.70.5 o./1s 29 grams n 1,4428-. (3) B.P. 70.5 70.5 C./l8 15 grams, n 1.4428. (4) Residue 56 grams, n 1.4430. (5) Solid carbon dioxide trap.

Fractions 1-4 (1.47 grams) corresponded to a yield of 22 percent based on unrecovered CF =CClF;

Physical properties of Fraction 2 were: B.P., 70.5" C./ 18 mm.; n 1.4428; d 2.1665. Calculated for 0 01 1 1: MR 48.21; M.W., 39 5, AgCl-l-Agl, g;/ sample, g. 1.694. Found: MR 48.70; MW.', 388, AgCl+AgI, g./sample, g., 1.697.

EXAMPLE 6 Reduction and dehaloge nation of CClF CCIFCF CClFI A three-necked 600 ml. flask containing 72 grams of percent zinc dustsuspended in ml. of ethyl alcohol was fitted to a distillation column, a mercury sealed wire stirrer and a dropping funnel; A solid carbon dioxide trap was connected to the column and the system was blanketed with nitrogen. The butane, grams, was added slowly to the refluxing ethanol whereupon a vigorous reaction, started. The product was removedthrough the column at a boiling point of approximately 50 C, as it formed. The mixture was refluxed for 1 hour after the bulk of the olefin had been removed and then material was removed until the boiling point of ethanol was reached, giving at best only a very small amount of additional olefin. Drowning of the pot residue yielded 17 grams of water insoluble, liquid. which contained chlorine and fluorine and was unsaturated to 2 percent KMnO About 5 grams of low boiling material with an infrared spectrum somewhat similar to perfluorobutadiene were caught in the solid carbon dioxide trap.

The crude butene was washed with ice water'to remove alcohol, dried over P 0 and distilled to yield:

(1) B.P.47.2 51 .5C./736mm. 9 grams, n 1.3220. (2) 515-515 C./736 4 grams, 1.3222.

(3) B.P. 51.5-52.0 C./736 25 grams, 1.3228.

(4) B.P. 5354 C./736 6 grams, 1.3288.

(5) Residue 12 grams.

EXAMPLE 7 Free radical addition reaction of CClF CCl I and CF =CClF It was reasoned that CCIF CCI I should be abetter chain transfer agent than CCIF CCIFI. This proved to be the case.

The most successful reaction .was carried out by placing 288 grams of CClF CCl I along with S'grams of benzoyl peroxide into a 450 ml. steel lecture cylinder. This was.

cooled in solid carbon dioxide, evacuated, and 89 grams of CF CCIF were condensed into the bomb. The contents were shaken thoroughly, after sealing and Warming to room temperature, and placed in a boiling water bath for 6" hours. Venting of'the cylinder gave 33 grams of unreacted olefin and 348 grams of a light pink liquid which was distilled to yield:

(1) B.P. 59-62 C./40 mm. 162 grams CCIF CCI I. (2) B.P. 5570-73 C./ mm. 140 grams. (3) Residue 18 grams. (4) Solid carbon dioxide trap 14 grams CF =CClF.

Moles iodide/olefin: Percent yield of butane 1.0 70 1.2 59 1.0 59

The lower yields in each case were accompanied by the formation of relatively larger amounts of higher polymers.

EXAMPLE 8 Free radical addition reaction of CCl FI and difluoroethylene The structure of the addition product was demonstrated as follows:

KMILOl C ClzFCH=G F2 C C12F C OOH 1 ,1 dich lore-1 ,3,3-trifluoro-3-iodopropane Dichlorofluoroiodomethane, 129 grams, washed free of iodine with aqueous thiosulfate and dried over CaCl and 2.8 grams of benzoyl peroxide were placed in a steel lecture cylinder fitted with a steel valve. The lecture cylinder was cooled in solid carbon dioxide and 36 grams of vinylidene fluoride were condensed into the cylinder from a tank using a pressure of approximately 20 p.s.i. The cylinder was shaken by hand and then placed in a furnace and heated at 85:3" C. for 15 hours. After heating, unreacted vinylidene fluoride was condensed into a steel lecture cylinder and the residual material was washed free of iodine with aqueous sodium thiosulfate. The crude product was dried over CaCl and distilled to yield:

(1) Material trapped in solid carbon dioxide 15.8 grams. (2) B.P. 30-35-37 C./ 100 mm. 44.5 grams unreacted CCI FI.

(3) B.P. 4044-45 C./15 mm. 68.2 grams. (4) Residue (solidified on cooling) 8.0 grams.

Conversion, based on CCI FI, 54 percent; yield 78 percent.

Several fractions prepared in the same way as Fraction 3 were combined and redistilled to yield:

(5) B.P. 4l4l.5 C./15 mm. 19.2 grams. (6) B.P. 41.5 C./l4 mm. 54.0 grams, n 1.4659. (7) B.P. 41.5 C./14 mm. 100.5 grams n 1.4659. (8) Residue 5.0 grams.

Properties of Fraction 7, CCl FCH CF I, were: B.P., 41.5 C. at 14 mm. of Hg (estimated 148 C. (760 mm.) F.P., 62.9, 62.9, 63.0 C.; range 0.3 C., n 1.4658; d 2.0956; MR calculated: 38.9. Found: 38.7; halogen calculated: 67.55 percent. Found, on the basis of total silver halide precipitate: 67.3 percent. This compound turned dark red on standing in a refrigerator.

EXAMPLE 9 3,3-dichloro-I ,1 ,3-trifluoropropene-1 Onto a five-fold excess of powdered KOH in a Claisen flask, heated by means of an oil bath to a temperature of l20il0 C., was dripped 117 grams of Vapors refluxing at 40-60" C. were collected. After all the halopropane had been added the system was pumped down to 2 mm., in order to recover unreacted starting material. The crude material was separated from water and dried over magnesium sulfate. Distillation of combined products from three typical runs based on a total of 362 grams of CCI FCH CF I yielded:

Grams (1) B.P. 4551.5-52.0 C./734 97 (2) B.P. 52-85 C./100 mm 20 (3) Residue (impure CCl FCH CF- I) 54 Conversion, based on CCI FCH CF I, 85 percent. Yield, 56 percent.

Distillation of several fractions prepared in the same way as Fraction 1 yielded:

Grams (4) Material in solid carbon dioxide trap 2.5 (5) B.P. 47.05l.5 C./741 mm. 3.0 (6) B.P. 51.552.0 C./741 mm. 32.0 (7) B.P. 52.052.2 C./741mm 68.0 (8) 52.2 C./741 mm. 8.5 (9) Residue 15.5

Properties of Fraction 7, CCL FCH=CF were: B.P., 52.0-52.2 C. at 741 mm. Hg, F.P., 102.0, 103.2 0, range 0.8 C.; n 1.3702; d 1.4504, MR calculated: 25.6. Found: 25.7. Molecular weight calculated: 165.0. Found: 164 (Dumas bulb).

EXAMPLE 10 Free radical addition reaction of CC1 I and hexaflaorobutadiene Hexafluorobutadiene, 91 grams, was sealed in a Pyrex ampoule with grams of CCl I and placed in a 5-bulb illuminator for five days at room temperature. The contents of the ampoule were distilled at 10 mm. to yield:

(1) Solid carbon dioxide trap 11 grams, recovered CiFi. (2) B.P. 60 to 62 C./l0 mm. 101 grams 0 01F I (3) B.P. 62 0./10 mm 22 grams (4) B.P. 62 0. 10 mm. so grams (5) Residue 5 grams.

The properties of Fraction 3 were, d 2.0827; n 1.4562; F.P. 24.3 to 24.7 C. MR for C CI F I: Found, 52.69; calculated, 52.87. Fraction 3 decolorized KMnO immediately and gave a precipitate with alcoholic AgNO after five minutes but did not react with NaI in acetone at room temperature.

The structure of the C Cl F I was indicated to be CCl CF CF=CFCF I by its infrared spectrum which showed a CF=CF vibration at 5.80 microns but no CF=CF vibration in the region of 5.55 to 5.65 microns.

EXAMPLE 11 Coupling by elimination of halogen with zinc dimerization of 1,2,2,4-tetrachloro-4-ioa'0perflu0r0butane one-halt hours afterwhich the mixture was stirre d for an additional eleven hours at room temperature (26?" 62.). The resulting liquid was decanted from the zinc-zinc halide mixture and the salt residue was washed with two 25 ml. portions of methylene chloride. The washings were combined with the main product and distilled to remove the solvents. A residue. of 79 grams remained which was then washed with water to remove traces of zinc halide. The clean liquid product remaining had to be dried under vacuum due to its great viscosity. Dis tillation yielded:

Fraction 1 corresponds to a yield of 60 percent of caclgF o. Physical properties of Fraction 1 were: B.P., 113 C./0.5 mm.; r1 1.4450; d gravitometer at 20 C., 1.975. Calculated for C Cl F t MR 76.60; C1, 49.5 percent; M.W., 569. Found: MR 78.9; CI, 48.9 percent; M.W., 555.

EXAMPLE l2 Thephysical. properties of the purest samples of novel compounds characterized are summarized below.

FORMAT I (M l u F r n -Cem und N Structural Formula) Source Z B.P. (boiling point at the prevailingatmospheric pressure) B.P./760 (boiling point corrected to one atmosphere) B.P. range F.P. t (equilibrium temperature of first appearance of crystals) F.P. dep. (depression from t to the point at which the materialwas estimated to be half frozen) F.P. calc. (estimated from cooling curve) M D (molecular refiractivity calculated using the Lorentz- Lorenz equation.)

(1 01 1 1 Propane,

l-iodo-1,3,3,3-tetrachlorotrifluoro-,

Source: CCl I+CClF=CF B.P 72.2 C./ mm. F.P. t -50.1 C. F.P. dep 0.1 C. d g./ml. 2.2265 n 1.5080 MR 48.4

10 C HCIF Butane, 4-chloro, 1,1,23, 3,4- hexafluoro, cr p FCF CHCI F B.P; 51.5 B.P./760 52-.6 B.P. range 0.5 C. d 9- (gravitometer at 20 C.) 1.531 n 1.3225 MR 25.8

C Cl F I Butane, 1,2,2,4-tetrachloro-4-iodopentafluoro-,

CClF CC1 CF CClFI B.P; 5 5.055.3- (L/ mm. F.P-. a Glass 14 V "D20 MR1:

C C I F I Butane, 1,2,4. trichloro 4. iodohezgafluorm,

CClF- CClFCF CClFI B.P. 70.5 C./18 mm. F.P. Glass d 2.1665 "D20 1 "T '1" "T""'f v C5C13F6I -pe ne, ode, ,5, loro. he afluoror,

CgCl'gFm 1,2,2,4,5,7,7,8 octachloro decafiuorooctane (CCIF CCI CF CCID Source: CClF CCl CF CClFI+zinc (acetic anhydridemethylene chloride) B.P. v 11 3 C./0.5 mm. d 1.975 (gravitometer) n I I 1.4450 MR 78.92

It will be obvious to those skilled in the art that many modifications may he made within the scope of themesent. invention without departing from. the spirit thereof; and the invention includes all such modifications.

I claim;

1. A process which comprises effecting the reaction under free radical conditions ofa compound having the formula in which}; is, selected from the group consisting. ofifluo; rine, chlorine, and perhaloalkyl radicals having not in excess of 8 carbon atoms and in which all halogen atoms have atomic weights not in excess of 35.46; and X and X are selected from the group consisting of fluorine and chlorine, at least one of X and X being chlorine; with a compound having the formula Y Y; in which Y is selected from the group consisting of hydrogen, fluorine, chlorine, and saturated and unsaturated perhaloalkyl radicals having not in excess of 12 carbon atoms and in which all halogen atoms have atomic weights not in excess of 35 .46; Y is selected from the group consisting of hydrogen, fluorine, and chlorine; and Y and Y are selected from the group consisting of fluorine and chlorine; at least one of the Y substituents being other than fluorine.

2. A process which comprises eflecting the reaction under free radical conditions of a compound having the formula in which X is selected from the group consisting of fluorine, chlorine, and polyhaloalkyl radicals having not in excess of 8 carbon atoms and in which all halogen atoms have atomic weights not in excess of 35.46; the polyhaloalkyl radicals having an average hydrogen content which is numerically no more than the carbon content; and X and X are selected from the group consisting of fluorine and chlorine, at least one of X and X being chlorine; with a compound having the formula which comprises effecting the reaction under free radical conditions of the compound CCl I with the compound CCIF=CF 4. A process for the preparation of the compound which comprises efiecting the reaction under free radical conditions of the compound CCIF CCIFI with the compound CClF=CF 5. A process for the preparation of the compound which comprises effecting the reaction under free radical conditions of the compound CClF CCl I with the compound CClF=CF 6. A process for the preparation of the compound CCI FCH CF I which comprises efiecting the reaction under free radical conditions of the compound CCI FI with the compound CH =CF 7. A process for the preparation of the compound CCI CF CF=CFCF I which comprises effecting the reaction under free radical conditions of the compound CCl I with the compound CF =CFCF=CF 8. A process which comprises efiecting the reaction under free radical conditions of a compound having the formula in which X is selected from a group consisting of fluorine, chlorine and polyhaloalkyl radicals having radicals having not in excess of 8 carbon atoms and in which all halogen atoms have atomic weights not in excess of 35.46; the polyhaloalkyl radicals having an average hydrogen content which is numerically no more than the carbon content; and X and X are selected from the group consisting of fluorine and chlorine, at least one of X and X being chlorine; with a compound having the formula l i. in which Y is selected from the group consisting of hydrogen, fluorine, chlorine and saturated and unsaturated perhaloalkyl radicals having not in excess of 12 carbon atoms and in which all halogen atoms have atomic weights not in excess of 35.46; Y is selected from the group consisting of hydrogen, fluorine and chlorine; and Y and Y are selected from the group consisting of fluorine and chlorine; at least one of the Y substituents being other than fluorine; to produce aliphatic iodohalocarbon addition product and reacting said iodohalocarbon addition product with a dehalogenating agent.

9. The process which comprises reacting under free radical conditions, the compound CCI FI with the compound CH =CF to produce the compound CCl FCH CF I and dehalogenating CCI FCH CF I with a dehalogenating agent selected from the group consisting of zinc and potassium hydroxide.

10. The process which comprises reacting under free radical conditions, the compound CCI FI with the compound CH ==CF to produce the compound CCI FCH CF I dehalogenating CCI FCH CF I with potassium hydroxide to produce CCl FCH=CF and oxidizing the product thus produced.

11. The process which comprises reacting under free radical conditions, the compound CClF CC1 I with the compound CC1F=CF to produce the compound dehalogenating CCIF CCI CF CClFI with zinc to produce (CClF2CCl3CF2cClF)2 and dechlorinating the product thus produced.

References Cited in the file of this patent UNITED STATES PATENTS 2,466,189 Waalkes Apr. 5, 1949 2,628,987 Ruh Feb. 17, 1953 2,628,988 Ruh Feb. 17, 1953 

1. A PROCESS WHICH COMPRISES EFFECTING THE REACTION UNDER FREE RADICAL CONDITIONS OF A COMPOUND HAVING THE FORMULA 